Chromable monoazo pyrazolone dye



Patented Oct. 28,' 19 47 a v NITED STATE-ES PATENT OFFICE I wz-Azafioo iGHBO AB E:MQ AZ P M LQ Walter Francis "Beech andglylqrdecai Mendoza, 'Blackley, Manchester, England, assignors ,to Imperial Chemical Industries ,Limi'tedp c. Q912- poration of Great Britain No Drawing. Application August-Z5,-1943,Serial :No. 499,998. In Great 'Britainrseptember 18,

.lfliai n. (01.;g -Afi3) 2 'iIYhepresent inventionrelates tothe manufac- -phenoxyphenyl).e3-:methyle5rpyrazolone ,and .1- -ture of. new monoazo. dyestuffs, and more particum-phenoXyphenyl-3=methyle5-pyrazo1one. -larly to. the manufacture of. chromabie moriQ zo f Thenew. dyestuffs of the present. inventionzare wool dyestuiis especiallysuitable for.:dyeing;by the eminentlyisuitableiior application. by themeta meta-chrome process. 5 ichrome process and .yieldstrong-dyeing's oisgood The meta chrome or chromate processv oidyefastness to ashing, milling, potting and .light,

ing is that wherein-La; mordant --dyestuii' is -om- -which. dyein'gs -are obtainahle. in -shades. ranging ployed in a singleloath simultaneously with the -::frormorange brownftmbluishred;

-chrome mordant,. e...g., sodium orpotassiumbi- *fIZhe:foilowinguexarnplesgin which thepartsare -chromate, =being thus 7 distinguished from the 1,0=byflweight,' il1ustrate but.are not 1ntended to. limit in which the operations of: dyeing andlmordantolderprocesses of dyeing with mordant. dyestuffs =-the' invention. v Example .1

ing are effected separately. :T-he meta-chrome or Y 6 24 part ,o -p: ph nyl r ri1hn -512 chromateprocess of-dyeing 1S accordinglyealso imwhmer Q(Pllfgmmd asrwidelsgniwdfb arieud.

{ as the singlelbathprocessj This process el -s'olved in "100 parts of ihot,water; j.loyl the addimwhmh the dyeing f mordantmg'may be tion of sufficient31.7% aqueous sodium'hydroxide garded as occurring-simultaneously offers great to make the Solution fljustialkahne to Clayton advantages. in my of time, ma r 3 Yellow paper. 8 par't'so'f anhydrous sodium car- .materialsoyer;the olderprocesses,just referred bonate areadded The Solution is 00018 d to The use 01.11118 meta-chrome or single "5;1o.o." it parts of.'6-ch1oro'-2 arninophenoltwee waver, attended by thedisadvant-ige I suiiihorficiiaditeguirmehfso :paitsoi titer that mordant dyestufiswhen applied in this Way d diazotised by theadditionpf 5. pa'rts of.3

,often tendto givepoorer colour values or weaker h I l a I ydroohloric ac d followed ,b a .4 arts of. so m shades for gwen- Qfidyestufi than, when nitrite .di'sso tdin .10. .partsjii w tefl Th'e. in

vthe,mordantingis carried out separately from-:.2 "sdlution so Obtained r is allowed to 11.111.111.17 e .thed ine- .T se t est av e nid :gsolut ion 'of thepym'zolone' duri [10 iii-tutti.

strengthby the meta-chrome process.

Sign torovercoflme this-disadvantage,- that' 715$) ITh'e mixtureis stirred for. hours and the new capablefif yielding shades piggqd .dyestufiniteredtimfanduried arse-d;

'l he iiew. lyestuif dyes wool by the .chro nate ..Accord1ng.,to the present invention new 3mm s0ikpmcessiynlorangemrdwnshagdes f g i mxi s 'mamemonQaZo WOOLdyestufis [are manufacturgd ness to washing milling pottingarid light. .by coupling .diazotised o-amino-phe nol and 9; fi y ab na mophthol monosulphonio acids,,,whi ch rnay oar ry ay abovenis lfobminablehby chdensing "simple substituents such as halogen andnitro, d 'a i nqdiphepyLWith ,g libe zpylgpc at ji flhg with a l-(diphenylyl or phenoXypheny1) -;-3-; .35 ethanoL (methyl or phenyl)e5 pyrazolone wherein the flE-mmplez phenyl groups may carry as substituents halogen,

; phonic acids theremaybe employed, for exam le, =.40 W th-zgliydra no p nyl) are dissolved in' 100 in accordance with this invention, 2 aminophenol- I Parts O h -WMQ I- by "the addition of sufficient -4-su1phonic acid, .Z-aminophenokG-sulphpnic ou od ium'l iydroxide to make the ...acid, 6 0111010 Z-aminophgnol;4- ul h i solution alkaline-to Clayton Yellow paper.

; 4-chloro+2eaminophenolefirsulphonic ;acid, .5 Agni- .troe2-aminopheno1-6-sulphonic acid, 6 nitro:-2- aminophenole-sulphonic acid and 1 lamino.-2- naphthol-4-sulphonic acid.

parts of anhydrous sodiurnicarbonate are added.

. The solution is cooled to 510 C. 4.68 parts of firynitrqrzr aminophenpl Lesulphonic acid are -si ermii fi o sis b wa .and cl' a e ise brlth .ad i io o w n ed. 3 ydro moriclaeidee Byway ofa 1- dipheny1y1-or ohe e i its of sodium nitrite in '10 parts of w ter 3-(me |,hylor phenyl)- -5-pyrazolone,there can be i i' I J 'mfi suffgredit'cl f fi u i thlsmventlon. for mstance, -.o+ l 1 .Qthe;abovepyrazolonesolntionlduring ,iori'iinuts. ylrseph y rapyra olone, 1- o diph y Y1i nfte'rlthel rnixturehas ,hee'n' stirred .ror. utters, ..,methyl 1 5 .pyrazolone, 1 p .phenoxyphenyl.-3 25;,parts oi sodium ,chlorideQareQadded to.. efiect w .methyl-5 pyrazolor e, l-(p 2'-ch1orophenoxy complete separation ofgthe"new dyestuff. Tlfhe phenyl)'-3-methy1-5-pyrazolone, 1- (p-el-chloro-fid latterfli-sdiltelzed ofli andidlfied 3.12.50 C.

The new dyestuff dyes wool by the meta-chrome process in orange-brown shades; the dyeings possess excellent fastness to washing, milling, potting and light.

Example 3 5.32 parts of l-p-phenoxypheny1-3-methyl-5- pyrazolone obtainable as described below, are dissolved in l parts of hot water, by the addition of 31.5% aqueous sodium hydroxide to make the solution faintly alkaline to Clayton Yellow paper. 8 parts of anhydrous sodium carbonate are added. The solution is then cooled to 510 C. and to the cooled solution is added a solution of diazotised l-chloro 2 aminophenol-G-sulphonic acid which has been made from 4.47 parts of 4- chloro-2-aminophenol-6-sulphonic acid by the same procedure as is described in Example 1 for 6 chloro-Z-aminophenoll-sulphonic acid. The mixture is stirred for 15 hours. The new dyestuff is filtered off and dried at 50 C.

When applied to wool by the meta-chrome process, the new dyestuif yields red shades of excellent fastness to washing, milling, potting and light.

The l-p-phenoxyphenyl -3- methyl -5- pyrazolone employed above is obtained by diazotising 4-amino-diphenyl ether, converting to the diazosulphonate (also referred to as the diazonium sulphonate) with sodium sulphite,, reducing with Zinc dust and glacial acetic acid to the corresponding hydrazino-fi-sulphonic acid, which is then converted by the action of hydrochloric acid to 4-hydrazinodiphenyl ether and the latter condensed with acetoacetic ester.

Example 4 are dissolved in 100 parts of hot water by the addition of sufficient 31.7% aqueous sodium hydroxide to make the solution faintly alkaline to Clayton Yellow paper. 1 part of anhydrous sodium carbonate is added. The solution is cooled to 5-10 C. To this cooled solution there is then added a solution of the diazo compound of 1-amino-2-naphthol4-sulphonic acid, the latter solution having been prepared by stirring 5 parts of the diazo oxide derived from l-amino- 2-naphthol4-sulphonic acid with 50 parts of water and sufiicient sodium bicarbonate to remove acidity to Congo red paper. The mixture is stirred for 15 hours. The new dye-stuff is then filtered off and dried at 50 C. This dyestuff yields bright bordeaux shades on wool when applied by the meta-chrome process. The dyeings thus produced possess excellent fastness to washing, milling, potting and light.

Example 5 6.01 parts of 1-(p-4'-chlorophenoxyphenyl) -3- methyl-5-pyrazolone, obtainable from 4-chloro- 4-aminodiphenyl ether by a similar process to that described in Example 4 for 1-(p-2-chlorophenoxyphenyl)-3-methyl-5-pyrazolone, are dissolved in 100 parts of hot water by the addition of 'sufficient 31.7% sodium hydroxide to make the solution faintly alkaline to Clayton Yellow paper. 8 parts of anhydrous sodium carbonate are added. The solution is then cooled to 5-10 C. 4.68 parts of 4-nitro-2-aminophenol-6-sulphonic acid are diazotised in 60 parts of water by the addition of 5 parts of 36% hydrochloric acid and 1.4 parts of sodium nitrite dissolved in 10 parts of water. The resulting diazo solution is then suffered to run into the above pyrazolone solution during 10 minutes. The mixture is stirred for 15 hours. The new dyestuif is then filtered off and dried at 50 C.

When wool is dyed by this dyestuff by use of the meta-chrome process, reddish-orange shades are obtained which exhibit excellent fastness in respect of washing, milling, potting and light.

Example 6 6.56 parts of 1-m-phenoxyphenyl-3-phenyl-5- pyrazolone, obtainable from S-aminodiphenyl ether by a similar process to that described in Example 3 in respect of 1-p-phenoxyphenyl-3-methyl-5-pyrazolone, are dissolved in parts of hot water by the addition of sufficient 31.7% aqueous sodium hydroxide to make the solution just alkaline to Clayton Yellow paper, 8 parts of anhydrous sodium carbonate are added. The solution is then cooled to 510 C. A diazo solution prepared from 4.68 parts of 4-nitro-2-aminophenol-fi-sulphonic acid in the manner described in the previous example is allowed to run into the above pyrazolone solution during 10 minutes. The mixture is stirred for 15 hours and the new dyestufi filtered off and dried at 50 C. This dyestulf, when applied to wool by the meta-chrome process, yields yellowish brown shades of excellent fastness to A diazo solution is prepared by agitating 4.68 parts of 6-nitro-2-aminophenol-l-sulphonic acid with 60 parts of water and 5 parts of 36% hydrochloric acid and subsequently adding a solution of 1.4 parts of sodium nitrite in 10 parts of water, the temperature being controlled at 5 C. 5 parts of 1-p-diphenylyl-3-methyl-5-pyrazolone are dissolved in 100 parts of water containing sufficient sodium hydroxide to render the resulting solution just alkaline to Clayton Yellow. To the pyrazolone solution 8 parts of soda ash are added. The above diazo solution is then let run into this pyrazolone solution during 10 minutes. After being stirred for 15 hours, the new dyestuiT is filtered 011 and dried at 50 C. It dyes wool by the meta-chrome process in orange-brown shades of excellent fastness to washing, milling, potting and light.

Example 8 4.68 parts of 6-nitro-2-aminophenol-4-sulphonic acid are stirred with 60 parts of water and 5 parts of 36% hydrochloric acid. A solution of 1.4 parts of sodium nitrite in 10 parts of water is then allowed to run in, the temperature being kept at 5 C. The resulting diazo solution is introduced during 10 minutes into a solution of 6.01 parts of 1-(p-l'-chlorophenoxyphenyl) -3-methyl-5-pyrazolone made by dissolving the latter in 100 parts of water containing sufficient sodium hydroxide to render the resulting solution just alkaline to Clayton Yellow and then adding 8 parts of soda ash. After stirring for 15 hours the dyestuff is filtered off and dried at 50 C. The new dyestuff dyes wool by the meta-chrome process in orange-brown shades. The dyeings possess excellent fastness to washing, milling, potting and light.

15 Number WALTER FRANCIS BEECH. 444 320 MORDECAI MENDOZA.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Schmid Apr. 2, 1940 Schmid Apr. 2, 1940 Schmid Apr. 2, 1940 Schmid Apr, 18, 1939 Fischer Nov, 10, 1936 Fischer July 30, 1935 FOREIGN PATENTS Country 'Dfit" France 1 Jan. 10, 1935 Germany Sept. 30, 1937 Switzerland Feb. 1, 1937 Germany Nov. 10, 1937 Switzerland May 1, 1937 Switzerland May 11, 1937 Great; Britain Mar. 27, 1936 

